US3198680A - Method of retreading tires using spray cement containing high concentration of activator - Google Patents

Method of retreading tires using spray cement containing high concentration of activator Download PDF

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Publication number
US3198680A
US3198680A US174270A US17427062A US3198680A US 3198680 A US3198680 A US 3198680A US 174270 A US174270 A US 174270A US 17427062 A US17427062 A US 17427062A US 3198680 A US3198680 A US 3198680A
Authority
US
United States
Prior art keywords
accelerator
parts
cement
activator
rubber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US174270A
Other languages
English (en)
Inventor
Alfred N Iknayan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Uniroyal Inc
Original Assignee
United States Rubber Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to NL289096D priority Critical patent/NL289096A/xx
Priority to BE626494D priority patent/BE626494A/xx
Application filed by United States Rubber Co filed Critical United States Rubber Co
Priority to US174270A priority patent/US3198680A/en
Priority to GB44825/62A priority patent/GB956344A/en
Priority to FR919072A priority patent/FR1341862A/fr
Priority to LU42954D priority patent/LU42954A1/xx
Application granted granted Critical
Publication of US3198680A publication Critical patent/US3198680A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/52—Unvulcanised treads, e.g. on used tyres; Retreading
    • B29D30/54—Retreading
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J121/00—Adhesives based on unspecified rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/52—Unvulcanised treads, e.g. on used tyres; Retreading
    • B29D30/54—Retreading
    • B29D2030/544—Applying an intermediate adhesive layer, e.g. cement or cushioning element between carcass and tread

Definitions

  • This invention relates to a method of retreading tires, and more particularly it relates to an improved method of adhering a new vulcanizable tread to a used cured tire carcass, with the aid of a spray cement composition containing an unusually high concentration of a migratory accelerator-activator.
  • the problem to which the invention is directed to solving arises in retreading tires in accordance with conventional practice by applying a new tread composed of rubber stock compounded for vulcanization to the buffed surface of a used, cured tire carcass.
  • a cement containing rubber, vulcanizing ingredients and solvent is usually applied to the buffed surface of the carcass prior to application of the new tread.
  • the assembly is then subjected to heat in a retreading mold to vulcanize the tread and at the same time cause it to adhere to the cementcoated carcass.
  • the new tread does not always adhere to the carcass as well as would be desired because it is in general quite difficult to obtain good adhesion to previously cured rubber.
  • the aldehyde-amine class of acceleratoractivator of the sulfur vulcanization of unsaturated rubbers is a conventional class of accelerator-activators made in known manner by reacting one or more aldehydes, such as acid aldehyde, butyraldehyde, alphaethyl betapropyl acrolein, or the like, with an amine, such as aniline, butylamine, etc.
  • aldehydes such as acid aldehyde, butyraldehyde, alphaethyl betapropyl acrolein, or the like
  • the tire carcass which may be recapped in accordance with the invention may be made of any conventional vulcanized rubber compositionwhether natural rubber or a synthetic rubber such as cis-polybutadiene or cispolyisoprene or a rubbery copolymer of a diene with a copolymerizable monomer such as styrene, acrylonitrile, vinylpyridine, or the like, or a mixture of such rubbers with or without other materials such as reclaimed rubber.
  • These rubbers or elastomers may be referred to as unsaturated rubbers or diene rubbers, in which category I include natural rubber and the homopolymers and copolymers containing a diene, as well as butyl rubber (a copolymer in which the diene is usually isoprene and the copolymerizable monomer is usually isobutylene), and unsaturated rubbers such as those made by copolymerizing ethylene and propylene or the like with conjugated or non-conjugated dienes, including open chain dienes such as hexadiene and cyclic dienes such as dicyclopentadiene. Butadiene-styrene rubber and natural rubber, and mixtures thereof, are especially preferred.
  • the carcass may of course be vulcanized in any suitable conventional manner, using such vulcanizing agents as sulfur along with the usual accelerators, antioxidants, fillers such as carbon black, and any other desired compounding ingredients in conventional amounts.
  • the new tread may similarly be based on any such diene rubber, of course in the unvulcanized state but compounded so as to be vulcanizable under the usual retreading conditions (275330 F. for 40 minutes to 8 hours) by reason of the presence, in conventional amounts, of sulfur or equivalent vulcanizing agent, accelerator, as well as carbon black and any other suitable desired compound ing ingredients.
  • the cement employed to adhere the new vulcanizable rubber tread to the cured carcass in accordance with the invention comprises parts (by weight) of a diene rubber as previously defined, from 0.5 to 5 parts of sulfur or equivalent vulcanizing agent, and from 0.5 to 5 parts of any suitable accelerator of sulfur vulcanization such as a guanidine accelerator and/or a carbon disulfide type accelerator (e.g., diphenyl guanidine, benzothiazyl disulfide, zinc dimcthyldithiocarbamatc, tetramethylthiuram disulfide, or any other suitable guanidine and/or carbon disulfide accelerator as disclosed for example in hemistry and Technology of Rubber by Davis and Blake, pages 302-303), together with sufficient conventional volatile rubber solvent (e.g., hydrocarbons, chlorinated hydrocarbons, ethers, ketones, etc., such as carbon tetrachloride, heptane, toluene, carbon disulfide,
  • the cement may further include the usual pigments or fillers such as carbon black, retarders, antioxidants and other desired conventional compounding ingredients. As thus far described the cement follows essentially conventional practice. However, the invention further contemplates the inclusion in the cement of an excess quantity of a migratory rubber-solvent soluble accelerator-activator selected from the group consisting of aldehydeamine condensation product, dibutylammonium oleate and morpholine (2,3,5,6-tetrahydro-l,4--oxazine).
  • a migratory rubber-solvent soluble accelerator-activator selected from the group consisting of aldehydeamine condensation product, dibutylammonium oleate and morpholine (2,3,5,6-tetrahydro-l,4--oxazine).
  • accelerator-activators of this kind may be mentioned Beutene (condensation product of one mole aniline, two moles butyraldehyde), A32 (butyraldehyde and butylidene aniline reaction product), Accelerator 803 (butyraldehyde-aniline), Accelerator 833 (butyraldehydebutylamine), Hepteen Base (heptaldehyde-aniline), Phenex (aniline-alphaethyl betapropyl acrolein), and Baralt (dibutylammonium oleate). These materials, as well as m-orpholine, are liquids.
  • Such ingredient is referred to' as migratory because it is capable of migrating or diffusing from one rubber layer to another especially under vulcanizing conditions. These chemicals accelerate and activate sulfur vulcanization of rubber.
  • the invention involves employing in the cement a far larger quantity of such migratory accelerator-activator of sulfur vulcanization than would ordinarily be used for the amount of rubber in the cement.
  • the present practice involves adding from 5 to 160 parts, preferably to 80 parts, and most preferably to parts, by weight of the defined accelerator-activator per 100 parts of rubber in the cement. This contrasts markedly to the comparatively small quantity of about 0.5 to 1 part that would conventionally be regarded as sufficient for the amount of rubber in the cement.
  • the cement formulated as described, is suitably sprayed onto the butfed tire carcass that it is desired to retread and/ or onto the undersurface of the new tread stock and after the cement is essentially dry the tread is applied to the carcass, pressed down firmly, and the assembly is enclosed in the retreading mold and subjected to the conventional vulcanizing conditions to adhere the vulcanizable tread to the cured carcass.
  • the tread adheres with remarkable tenacity to the cured carcass and there is an unprecedented freedom from weak spots or poorly adhered areas.
  • the adhesive bond is especially remarkable for the manner in which it maintains its strength even at elevated temperatures.
  • many conventional retreaded tires adhesion may not be noticeably lacking at ordinary temperatures, but when high temperatures are developed at the interface as a result of high speed operation weaknesses typically appear at the interface and separation of the tread soon occurs.
  • tires retreaded in accordance with this invention maintain good tread adhesion even at elevated temperatures.
  • the excellent physical properties of the adhesive bond produced in the present method is especially surprising in view of the fact that ordinarily the amount of rubber used in the present cement, if compounded with the large quantity of accelerator-activator here employed, would upon subjecting to vulcanizing conditions become so badly softened and/or peptized that it could not even be handled on conventional mixing equipment. It was therefore indeed unexpected to find that a cement compounded in this manner and used as described would form an adhesive film having excellent physical properties.
  • accelerator-activator in conventional amounts and in amounts slightly in excess of conventional tends to render the cement so readily vulcanizable that the cement gels or prevulcanizes even on standing at room temperature, as evidenced by marked increase in viscosity and early solidification.
  • a cement containing 2 parts of butyraldehydeaniline, having an initial viscosity of 40 seconds at 84 F. will set up spontaneously to a solid state in three days exposure to a temperature of 160 F.
  • Example A used, worn tire made of cured SBR is buffed to remove the remains of the old tread and to present a clean surface of definite contour to receive a new tread.
  • a strip of unvulcanized new tread stock of the following composition is provided:
  • a retreading cement is prepared in accordance with the following formulation:
  • the cement is sprayed onto the buffed surface of the cured carcass, and allowed to dry until it is tacky to the touch.
  • the new tread is applied, pressed down firmly, and enclosed in the retreading mold where it is heated at 300 F. for 2 hours.
  • the adhesion of the tread is excellent, both at room temperature and elevated temperature.
  • the following table shows the relationship between the concentration of accelerator-activator in the cement and the adhesion, evaluated both at room temperature and at elevated temperature. These tests were made by lamihating a vulcanizable stock representing a tread to a previously cured stock representing a carcass, with the aid of a cement of the kind exemplified above, the concentration of accelerator-activator (butyraldehydeaniline) lJClilg varied from 0 part to parts as shown in the 1 Stock failures rather than interfacial failures.
  • cements containing 5 or more parts of the accelerator-activator have adequate stability, whereas cements containing less than this are not suificiently stable.
  • accelerator-activator gives a significant improvement in adhesion, optimum bonding is reached in the 2040 part level. We see from the adhesion data'that the interface is still well bonded with as much as 160 parts accelerator-activator, but for reasons of economy and to avoid peptizing the adjacent stock we do not ordinarily use more than 160 parts.
  • the preferred upper limit on the amount of accelerator-activator is 80 parts.
  • a method of adhering a new tread comprising a vulcanizable diene rubber composition to a cured tire comprising a diene rubber composition comprising in combination the steps of providing a re-treading cement of spraying consistency comprising, by weight, 100 parts of diene rubber, 0.5 to 5 parts of sulfur, 0.5 to 5 parts of accelerator of sulfur vulcanization, 1500 to 4000 parts of rubber solvent, and 5 to 160 parts of a migratory accelerator-activator selected from the group consisting of aldehydearnine accelerator-activators, dibutylammonium oleate and morpholine, the said cement being stable at room temperature, spraying said cement on a butter surface of said carcass, applying the said new tread in an unvulcanized condition, and subjecting the assembly to vulcanizing conditions.
  • a re-treading cement of spraying consistency comprising, by weight, 100 parts of diene rubber, 0.5 to 5 parts of sulfur, 0.5 to 5 parts of accelerator of sulfur vulcanization
  • diene rubber is selected from the group consisting of butadienestyrene rubber and natural rubber.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Tyre Moulding (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US174270A 1962-02-19 1962-02-19 Method of retreading tires using spray cement containing high concentration of activator Expired - Lifetime US3198680A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NL289096D NL289096A (en, 2012) 1962-02-19
BE626494D BE626494A (en, 2012) 1962-02-19
US174270A US3198680A (en) 1962-02-19 1962-02-19 Method of retreading tires using spray cement containing high concentration of activator
GB44825/62A GB956344A (en) 1962-02-19 1962-11-27 Improvements in pneumatic tyres
FR919072A FR1341862A (fr) 1962-02-19 1962-12-18 Procédé de rechapage de pneumatiques
LU42954D LU42954A1 (en, 2012) 1962-02-19 1962-12-29

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US174270A US3198680A (en) 1962-02-19 1962-02-19 Method of retreading tires using spray cement containing high concentration of activator

Publications (1)

Publication Number Publication Date
US3198680A true US3198680A (en) 1965-08-03

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Family Applications (1)

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US174270A Expired - Lifetime US3198680A (en) 1962-02-19 1962-02-19 Method of retreading tires using spray cement containing high concentration of activator

Country Status (5)

Country Link
US (1) US3198680A (en, 2012)
BE (1) BE626494A (en, 2012)
GB (1) GB956344A (en, 2012)
LU (1) LU42954A1 (en, 2012)
NL (1) NL289096A (en, 2012)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3513047A (en) * 1968-09-26 1970-05-19 Tread Rubber Corp Process for producing cushionless retreaded tires
US4371411A (en) * 1978-05-30 1983-02-01 Bridgestone Tire Company Limited Method of adhering unvulcanized rubber to vulcanized rubber through vulcanization
US20040079459A1 (en) * 2001-10-30 2004-04-29 Claudina Veas Method for retreading a tire
US11247424B1 (en) 2016-12-13 2022-02-15 Bridgestone Americas Tire Operations, Llc Methods for retreading tires

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1893869A (en) * 1931-01-07 1933-01-10 Harold A Morton Vulcanizable compound and process for preparing game
US2431001A (en) * 1945-04-27 1947-11-18 Du Pont Coated fabric
US2906740A (en) * 1956-06-08 1959-09-29 Du Pont Vulcanizable elastomer pellet and process of forming unscorched extrudate
US2948320A (en) * 1955-05-02 1960-08-09 Exxon Research Engineering Co Co-vulcanized butyl rubber with highly unsaturated rubbers by amino compounds
US2976910A (en) * 1958-12-19 1961-03-28 Bandag Inc Method and material for retreading pneumatic tire casings
US3035953A (en) * 1958-03-24 1962-05-22 Phillips Petroleum Co Laminates of aluminum and solid polymers of 1-olefins
US3111451A (en) * 1956-12-31 1963-11-19 Bell Telephone Labor Inc Method of bonding polymers and articles produced

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1893869A (en) * 1931-01-07 1933-01-10 Harold A Morton Vulcanizable compound and process for preparing game
US2431001A (en) * 1945-04-27 1947-11-18 Du Pont Coated fabric
US2948320A (en) * 1955-05-02 1960-08-09 Exxon Research Engineering Co Co-vulcanized butyl rubber with highly unsaturated rubbers by amino compounds
US2906740A (en) * 1956-06-08 1959-09-29 Du Pont Vulcanizable elastomer pellet and process of forming unscorched extrudate
US3111451A (en) * 1956-12-31 1963-11-19 Bell Telephone Labor Inc Method of bonding polymers and articles produced
US3035953A (en) * 1958-03-24 1962-05-22 Phillips Petroleum Co Laminates of aluminum and solid polymers of 1-olefins
US2976910A (en) * 1958-12-19 1961-03-28 Bandag Inc Method and material for retreading pneumatic tire casings

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3513047A (en) * 1968-09-26 1970-05-19 Tread Rubber Corp Process for producing cushionless retreaded tires
US4371411A (en) * 1978-05-30 1983-02-01 Bridgestone Tire Company Limited Method of adhering unvulcanized rubber to vulcanized rubber through vulcanization
US20040079459A1 (en) * 2001-10-30 2004-04-29 Claudina Veas Method for retreading a tire
US7128794B2 (en) * 2001-10-30 2006-10-31 Michelin Recherche Et Technique S.A. Method for retreading a tire
US11247424B1 (en) 2016-12-13 2022-02-15 Bridgestone Americas Tire Operations, Llc Methods for retreading tires

Also Published As

Publication number Publication date
GB956344A (en) 1964-04-22
BE626494A (en, 2012)
LU42954A1 (en, 2012) 1963-03-01
NL289096A (en, 2012)

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